US4780289A - Process for nitrogen oxides reduction and minimization of the production of other pollutants - Google Patents

Process for nitrogen oxides reduction and minimization of the production of other pollutants Download PDF

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Publication number
US4780289A
US4780289A US07/050,198 US5019887A US4780289A US 4780289 A US4780289 A US 4780289A US 5019887 A US5019887 A US 5019887A US 4780289 A US4780289 A US 4780289A
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United States
Prior art keywords
effluent
nitrogen oxides
treatment agent
pollutants
treatment
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US07/050,198
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English (en)
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William R. Epperly
John H. O'Leary
James C. Sullivan
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Fuel Tech Inc
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Fuel Tech Inc
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Application filed by Fuel Tech Inc filed Critical Fuel Tech Inc
Priority to US07/050,198 priority Critical patent/US4780289A/en
Assigned to FUEL TECH, INC., A CORP. OF MA reassignment FUEL TECH, INC., A CORP. OF MA ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: EPPERLY, WILLIAM R., O'LEARY, JOHN H., SULLIVAN, JAMES C.
Priority to US07/132,801 priority patent/US4830839A/en
Priority to GB8825253A priority patent/GB2225001B/en
Priority to HU882855A priority patent/HUT50294A/hu
Priority to CA000560672A priority patent/CA1311107C/en
Priority to PCT/US1988/000724 priority patent/WO1988006487A1/en
Priority to YU00448/88A priority patent/YU44888A/xx
Priority to DE198888903063T priority patent/DE304478T1/de
Priority to DE88903063T priority patent/DE3881984T2/de
Priority to EP88903063A priority patent/EP0304478B1/de
Priority to AU14993/88A priority patent/AU1499388A/en
Priority to AT88903063T priority patent/ATE90883T1/de
Priority to PL27105588A priority patent/PL271055A1/xx
Priority to DE1988905072 priority patent/DE313648T1/de
Priority to AT88905072T priority patent/ATE116950T1/de
Priority to HU883960A priority patent/HU205586B/hu
Priority to AU18074/88A priority patent/AU594299B2/en
Priority to PCT/US1988/001500 priority patent/WO1988008824A1/en
Priority to EP88905072A priority patent/EP0313648B1/de
Priority to DE19883852747 priority patent/DE3852747T2/de
Priority to JP50477488A priority patent/JP2817929B2/ja
Priority to CA 566246 priority patent/CA1309230C/en
Priority to YU92888A priority patent/YU92888A/xx
Priority to PL27242588A priority patent/PL272425A1/xx
Priority to DD88315758A priority patent/DD274171A5/de
Priority to PT87493A priority patent/PT87493B/pt
Priority to GR880100315A priority patent/GR880100315A/el
Priority to MX1145588A priority patent/MX167771B/es
Priority to ES8801499A priority patent/ES2006659A6/es
Priority to CN88102929A priority patent/CN1030193A/zh
Priority to US07/207,382 priority patent/US4902488A/en
Priority to US07/411,902 priority patent/US5017347A/en
Application granted granted Critical
Publication of US4780289A publication Critical patent/US4780289A/en
Priority to DK614888A priority patent/DK614888D0/da
Priority to FI885103A priority patent/FI885103A/fi
Priority to NO884950A priority patent/NO884950L/no
Priority to DK731788A priority patent/DK731788A/da
Priority to NO89890147A priority patent/NO890147L/no
Priority to FI890165A priority patent/FI88464C/fi
Priority to US07/416,317 priority patent/US5057293A/en
Assigned to FUEL TECH, INC. reassignment FUEL TECH, INC. SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: NALCO FUEL TECH, INC.
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00054—Controlling or regulating the heat exchange system
    • B01J2219/00056—Controlling or regulating the heat exchange system involving measured parameters
    • B01J2219/00058—Temperature measurement
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Definitions

  • the present invention relates to a process for the reduction of nitrogen oxides (NO x ) in the effluent, especially the oxygen-rich effluent, from the combustion of a carbonaceous fuel while minimizing the production of other pollutants, such as ammonia (NH 3 ) and/or carbon monoxide (CO).
  • NO x nitrogen oxides
  • NH 3 ammonia
  • CO carbon monoxide
  • Carbonaceous fuels can be made to burn more completely, and with reduced emissions of carbon monoxide and unburned hydrocarbons, when the oxygen concentrations and air/fuel ratios employed are those which permit high flame temperatures.
  • temperatures above about 2000° F. and typically about 2200° F. to about 3000° F. are generated.
  • thermal NO x the temperatures being so high that free radicals of oxygen and nitrogen are formed and chemically combine as nitrogen oxides.
  • Nitrogen oxides can form even in circulating fluidized bed boilers which operate at temperatures which typically range from 1300° F. to 1700° F.
  • Nitrogen oxides are troublesome pollutants which are found in the combustion effluent streams of boilers when fired as described above, and comprise a major irritant in smog. It is further believed that nitrogen oxides can undergo a process known as photo-chemical smog formation, through a series of reactions in the presence of sunlight and hydrocarbons. Moreover, nitrogen oxides comprise a significant contributor to acid rain.
  • the present invention meets this need and provides the ability to control NO x in concert with other pollutants under varying as well as constant load conditions in a manner and to a degree never before available.
  • the process comprises introducing (most commonly by injecting) a NO x reducing treatment agent into an effluent according to a NO x reducing treatment regimen under conditions such that the treatment agent is operating on the high temperature or right side of its nitrogen oxides reduction versus effluent temperature curve, especially on the high temperature or right side of the curve plateau.
  • An object of the present invention is to achieve significant reductions in nitrogen oxides levels without the production of substantial amounts of other pollutants by effecting a treatment regimen while monitoring the condition of the effluent and, when a change in effluent condition is observed, adjusting the treatment regimen by varying one or more treatment regimen parameters to effect an adjusted treatment regiment which operates on its nitrogen oxides reduction versus effluent temperature curve further to the right than did the originally-effected treatment regimen on its nitrogen oxides reduction versus effluent temperature curve.
  • Another object of the present invention is to achieve significant reductions in nitrogen oxides levels without the production of substantial amounts of other pollutants by determining the nitrogen oxides reduction versus effluent temperature curves for each of a plurality of treatment regimen and effecting the treatment regimen which will, under the effluent condition currently existing, operate furthest to the right on its curve than the others.
  • Still another object of the present invention is to achieve significant reductions in nitrogen oxides levels without the production of substantial amounts of other pollutants by effecting a treatment regimen and adjusting the position of introduction of the treatment regimen to cause the introduction to be performed at a different effluent temperature and thereby effect the treatment regimen to operate more towards the right side of the plateau of its nitrogen oxides reduction versus effluent temperature curve.
  • Yet another object of the present invention is to achieve significant reductions in nitrogen oxides levels without the production of substantial amounts of other pollutants by effecting a treatment regimen under conditions effective to reduce the effluent nitrogen oxides concentration and then varying one or more treatment regimen parameters to shift the treatment regimen nitrogen oxides reduction versus effluent temperature curve towards the right side of the curve plateau.
  • Still another object of the present invention is to achieve significant reductions in nitrogen oxides levels without the production of substantial amounts of other pollutants by effecting a treatment regimen, determining the position on its nitrogen oxides reduction versus effluent temperature curve at which the treatment regimen is operating and varying one or more treatment regimen parameters so that the varied treatment regimen is operating on its nitrogen oxides reduction versus effluent temperature curve further to the right.
  • Another object of the present invention is to achieve significant reductions in nitrogen oxides levels without the production of substantial amounts of other pollutants by effecting a treatment regimen and varying one or more treatment regimen parameters to drive the reaction or series of reactions by which the treatment regimen reduces nitrogen oxides towards a reduction of the production of other pollutants while substantially maintaining the level of nitrogen oxides reductions.
  • Yet another object of the present invention is to achieve significant reductions in nitrogen oxides levels without the production of substantial amounts of other pollutants by effecting a treatment regimen while monitoring boiler operating load and varying one or more treatment regimen parameters when a significant change in boiler load is observed to effect an adjusted treatment regimen.
  • Another object of the present invention is to achieve signficant reductions in nitrogen oxides levels without the production of substantial amounts of other pollutants by effecting a treatment regimen under conditions where the treatment regimen is operating on its nitrogen oxides reduction versus effluent temperature curve at a position to the right of the curve plateau and adjusting one or more treatment regimen parameters to operate the adjusted treatment regimen towards its curve plateau.
  • Still another object of the present invention is to ascertain the condition of the effluent by effecting a treatment regimen, measuring the condition of the effluent and, by reference to the nitrogen oxides reduction versus effluent temperature curve, determine what the condition of the effluent was prior to the treatment regimen being effected.
  • FIGS. 1 and 1a graphically represent the results of Example I
  • FIG. 2 graphically represents the results of Examples IIa, IIb and IIc;
  • FIGS. 3a-c graphically represent the results of Examples IIIa, IIIb and IIIc;
  • FIGS. 3d-f graphically represent the results of Examples IIIa, IIIb and IIIc presented as described below.
  • FIG. 4 graphically represents the results of Example IV.
  • nitrogen oxides reduction versus effluent temperature curve refers to a plot of the data points generated when a treatment regimen is effected by introducing a treatment agent into an effluent over a range of effluent temperatures and the nitrogen oxides reduction at each introduction temperature is measured (and usually expressed in terms of percent of baseline);
  • curve plateau refers to that region of a nitrogen oxides reduction versus effluent temperature curve where the NO x reduction is substantially maximized over a range of temperatures and preferably encompasses at least two data points (of course a skilled artisan will recognize that a curve plateau will not necessarily be flat due to "data scatter” and other practical data generation effects);
  • high temperature side or “right side” refer to any point on the subject nitrogen oxides reduction versus effluent temperature curve which represents the reduction achieved when a treatment regimen is effected at a higher temperature than the original temperature at which a treatment regiment was effected;
  • treatment regimen refers to the introduction (such as by injection) of a treatment agent into an effluent and the conditions under which the treatment agent is introduced, such as treatment agent components (by which is meant the ingredients or chemical formulation of the treatment agent), treatment agent dilution (by which is meant the concentration of treatment agent components when the treatment agent used comprises a solution), relative presence of treatment agent components (by which is meant the relative weight ratio or fractions of the components which form the chemical formulation which makes up the treatment agent), etc.;
  • treatment agent components by which is meant the ingredients or chemical formulation of the treatment agent
  • treatment agent dilution by which is meant the concentration of treatment agent components when the treatment agent used comprises a solution
  • relative presence of treatment agent components by which is meant the relative weight ratio or fractions of the components which form the chemical formulation which makes up the treatment agent
  • treatment agent refers to a composition comprising at least one reductant chemical, i.e., a pollution reducing chemical capable of reducing NO x , sulfur oxides (SO x ) or other pollutants by facilitating a reaction (the term “reaction” will be understood to refer to a single reaction or a series of reactions), and, preferably, with a solvent;
  • reductant chemical i.e., a pollution reducing chemical capable of reducing NO x , sulfur oxides (SO x ) or other pollutants by facilitating a reaction
  • reaction will be understood to refer to a single reaction or a series of reactions
  • condition condition or “condition of the effluent” refers to the existing state of any one or more parameters which can be used to characterize the effluent, such as temperature, nitrogen oxides level, ammonia level, carbon monoxide level, excess oxygen level, sulfur oxides level, etc.;
  • normalized stoichiometric ratio refers to the ratio of the concentration of reducing-radicals such as NH x radicals (NH x radicals, with x being an integer, are believed to be the moiety contributed by the treatment agent which facilitates the series of reactions resulting in NO x breakdown) to the concentration of nitrogen oxides in the effluent and can be expressed as [NH x ]/[NO x ] (alternatively, the molar ratio of the treatment agent to the NO x concentration can be used in place of NSR when the chemistry of reduction is not well defined; the term NSR as used herein will also be understood to encompass molar ratio when appropriate);
  • oxygenated hydrocarbon refers to a hydrocarbon which contains oxygen or an oxygen-containing group
  • saccharide refers to a number of useful saccharide materials which are capable of decreasing the NO x concentration in an effluent under conditions as described herein, including non-reducing and reducing water soluble mono-saccharides and the reducing and non-reducing polysaccharides and their degradation products, such as pentoses including aldopentoses, methyl pentoses, keptopentoses like xylose and arabinose, deoxyaldoses like rhaminose, hexoses and reducing saccharides such as aldo hexoses like glucose, galactose and mannose, ketohexoses like fructose and sorbose, disaccharides like lactose and maltose, non-reducing disaccharides like sucrose and other polysaccharides such as dextrin and raffinose, hydrolyzed starches which contain as their constituents oligosaccharides, and water dispersible polysaccharides;
  • pentoses including aldopentoses
  • amino acid refers to any organic acid in which at least a portion of the nonacid hydrogen has been replaced by one or more amino groups and which therefore shows both basic and acidic properties
  • protein refers to a polymeric compound comprising the polymerization or condensation product of amino acids
  • “skimmed milk” refers to milk having some or all of the fat removed.
  • “powdered milk” refers to non-fat dry milk, available commercially as Carnation Instant Non-Fat Dry Milk from Carnation Company of Los Angeles, Calif.
  • Appropriate treatment agents known as being effective at the reduction of nitrogen oxides include aqueous solutions of urea or ammonia, or gaseous ammonia, as disclosed by copending and commonly assigned U.S. patent application entitled “Reduction of Nitrogen- and Carbon-Based Pollutants Through the Use of Urea Solutions” having Ser. No. 784,826, filed in the name of Bowers on Oct. 4, 1985; copending and commonly assigned U.S. patent application entitled “Reduction of Nitrogen Based Pollutants Through the Use of Urea Solutions Containing Oxygenated Hydrocarbon Solvents" having Ser. No. 784,828, filed in the name of Bowers on Oct. 4, 1985 now U.S. Pat. No. 4,719,092; and U.S. Pat. No. 3,900,554 to Lyon, the disclosures of each of which are incorporated herein by reference.
  • treatment agents which comprise other compositions such as hexamethylenetetramine (HMTA), ethylene glycol, furfural, hydrocarbons, sugar, milk or skimmed milk, amino acids, proteins and monoethanolamine are disclosed as being effective at the reduction of nitrogen oxides in an effluent in combination with aqueous solutions of urea or ammonia in several disclosures.
  • HMTA hexamethylenetetramine
  • hydrocarbons such as an oxygenated hydrocarbon, a nitrogenated hydrocarbon like a hydroxy amino hydrocarbon or hydrocarbon peroxide
  • the nitrogen oxides reduction versus effluent temperature curve for a treatment regimen comprises a curve plateau, which, as described above, indicates where the NO x reduction elicited by the treatment regimen is maximized and that such maximum level is substantially maintained over a range of effluent temperatures.
  • An exemplary nitrogen oxides reduction versus effluent temperature curve for a treatment regimen disclosed as being an effective nitrogen oxides reducing treatment regimen is reproduced as FIG. 1.
  • FIG. 1 is the nitrogen oxides reduction versus effluent temperature curve for a treatment regimen comprising a treatment agent which comprises 10% by weight of urea, 4% by weight of hexamethylenetetramine and 10% by weight of furfural, which is injected into an effluent at the rate of 300 ml/hr. and an excess of oxygen in the effluent of 3.0% by volume.
  • the curve plateau for FIG. 1 will be recognized as the nitrogen oxides reduction achieved by effecting the disclosed treatment regimen between effluent temperatures of 1530° F. and 1680° F. (the skilled artisan will recognize that due to normal experimental variations, the curve plateau, and indeed the nitrogen oxides reduction versus effluent temperature curve itself, for any given treatment regimen will show minor variations each time it is experimentally derived). This temperature range, it will be observed, provides the maximum nitrogen oxides reduction for this treatment regimen.
  • nitrogen oxides reduction Merely maximizing the nitrogen oxides reduction, though, is not enough. Of concern is not only the nitrogen oxides level in the effluent, but also the level of other pollutants, such as ammonia and carbon monoxide which are often produced in the NO x reducing process. For instance, when NO x reduction is achieved by using treatment agent comprising urea or ammonia alone, ammonia is produced, whereas when NO x reduction is achieved by use of a treatment agent comprising urea or ammonia enhanced with a disclosed enhancer, or by use of a hydrocarbon treatment agent, ammonia and carbon monoxide are produced.
  • FIGS. 1 and 1a graphically represent the results of Example I.
  • FIG. 1 reproduces the nitrogen oxides reduction versus effluent temperature curve for a treatment regimen which is effective at reducing the nitrogen oxides level in an effluent from the combustion of a carbonaceous fuel.
  • FIG. 1a reproduces that same nitrogen oxides reduction versus effluent temperature curve and further has superimposed thereon the ammonia and carbon monoxide levels observed at each point on the curve. It can be seen that although NO x reduction is maximized throughout the curve plateau (i.e., injection in the effluent temperature range of about 1530° F. to about 1680° F.), performing the injection further to the right on the curve plateau (i.e., at higher temperatures in the plateau temperature range) leads to substantially reduced production of ammonia and carbon monoxide.
  • Operation further to the right on the curve can be achieved in one of two methods.
  • the position on the curve at which the treatment regimen being used is being effected can be translated further to the right by effecting the treatment regimen at a higher effluent temperature. It will readily be observed by reference to FIGS. 1 and 1a that effecting the treatment regimen at a higher effluent temperature will translate the position of operation on the curve further to the right, thereby reducing the production of other pollutants while maintaining maximum nitrogen oxides reduction.
  • Effecting the treatment regimen at a higher effluent temperature can be accomplished by performing the treatment agent introduction at a location where the effluent temperature is higher, i.e., at a location upstream (or closer to the flame zone) from the original introduction location.
  • This method for effecting the treatment regimen at a higher effluent temperature can oftimes be impractical because access to the boiler interior is often limited to specific points, due to water tubing, etc. Introduction at a location where the effluent temperature is at a desired level, therefore, is often not possible. Operation at a much higher effluent temperature can translate the position of operation on the curve too far to the right and off the plateau, thereby decreasing NO x reduction.
  • Altering the operating load of the boiler i.e., fuel supply rate
  • altering the boiler operating load is not preferred because the effluent condition is altered in more than the temperature parameter, as will be discussed in more detail below.
  • Nitrogen oxides level, as well as other parameters such as ammonia level and carbon monoxide level are altered along with effluent temperature.
  • the boiler operating load is usually maintained at a certain level to produce a specific, required output and is not available as a factor which can be altered to achieve NO x reduction.
  • the second method for operating further to the right on the curve is to vary one or more of the parameters of the treatment regimen being effected.
  • the varied parameter can be the components of the treatment agent, the dilution of the treatment agent when in solution with a concommitant variation in treatment again introduction rate to maintain the NSR of the treatment regimen (as discussed above, the NSR refers also to the molar ratio of the treatment agent to the baseline nitrogen oxides level, where appropriate), the relative presence of treatment agent components, or combinations of any of the above.
  • the original nitrogen oxides reduction versus effluent temperature curve is replaced by the nitrogen oxides reduction versus effluent temperature curve for the varied treatment regimen. Selection of the parameter(s) to be varied and in what way they are varied can replace the original curve with a curve which is "shifted" to the left, thereby leading to operation on the shifted curve at a position further to the right.
  • FIG. 2 provides the nitrogen oxides reduction versus effluent temperature curve plateau for three treatment regimens which each comprise introducing a treatment agent into an effluent over a range of effluent temperatures and at an introduction rate of 300 ml/hr. and an excess of oxygen of 3.0% by volume.
  • the treatment agent introduced for the first treatment regimen comprises an aqueous solution of 10% urea and 15% furfural;
  • the treatment agent introduced for the second treatment regimen comprises an aqueous solution of 10% urea;
  • the treatment agent introduced for the third treatment regimen comprises an aqueous solution of 10% urea and 15% ethylene glycol.
  • the treatment regimen being effected comprises a treatment agent which is an aqueous solution of 10% urea
  • the effluent temperature at the treatment location is 1755° F.
  • varying the treatment regimen by varying the treatment agent components by injecting 15% furfural with the 10% urea replaces the original curve with a curve at which introduction at that effluent temperature operates further towards the right side of the curve plateau.
  • the treatment regimen being effected comprises a treatment agent which is an aqueous solution of 10% urea and 15% furfural, and the effluent temperature at the point of introduction is 1665° F., thereby operating near the midpoint of the treatment regimen nitrogen oxides reduction versus effluent temperature curve plateau, then varying the treatment regimen to vary the treatment agent to replace the 15% furfural with 15% ethylene glycol replaces the original curve with a curve at which introduction at that effluent temperature operates further towards the right side of the curve plateau.
  • the two methods for operating further to the right on the curve plateau disclosed according to the present invention are not mutually exclusive, but can in fact be combined.
  • the effluent temperature can be varied along with one or more treatment regimen parameters.
  • varying one or more treatment regimen parameters serves to produce an adjusted (or new) treatment regimen which will have a different (or shifted) nitrogen oxides reduction versus effluent temperature curve compared to the original treatment regimen.
  • the nitrogen oxides reduction versus effluent temperature curve for a plurality of treatment regimens such as aqueous solutions comprising 10% by weight of urea and varying amounts of ethylene glycol which are introduced into an effluent over a range of effluent temperatures and at an introduction rate of 300 ml/hr and an excess of oxygen of 3.0% by volume, can be plotted.
  • the data which comprises the plots can then be compared to determine which treatment regimen should be effected according to this invention for the effluent condition existing at the injection location.
  • FIGS. 3d-3f graphically express the nitrogen oxides reduction, ammonia level and carbon monoxide level for each of the three treatment regimens represented by FIGS. 3a-3c, at three particular location of introduction effluent temperatures. If the effluent temperature at the introduction location is 1560° F., the desired treatment regimen, therefore, is the regimen which comprises the treatment agent having 15% ethylene glycol, as illustrated in FIG. 3d. If the effluent temperature at the introduction location is 1650° F., the desired treatment regimen, therefore, is the regimen which comprises the treatment agent having 10% ethylene glycol, as illustrated in FIG. 3e (the 15% ethylene glycol treatment regimen is not desired at 1650° F. because, although FIG.
  • the desired treatment regimen is the regimen which comprises the treatment agent having 5% ethylene glycol, as illustrated in FIG. 3f, because both the 10% ethylene glycol and 15% ethylene glycol treatment regimens are operating to the right and off their curve plateau.
  • Another advantageous aspect of the present invention is in the situation where an effluent from the combustion of a carbonaceous fuel is required to have no more than a maximum level of another pollutant, such as ammonia and/or carbon monoxide.
  • the process of this invention can be used to achieve the maximum possible NO x reduction, or a target level of NO x reduction, while maintaining the level of such other pollutants under such maximum level.
  • NSR normalized stoichiometric ratio
  • the NSR is increased until the first of such other pollutants reaches its maximum level. In this way, the highest possible NO x reduction can be achieved while maintaining the effluent in a condition which is below the maximum level for other pollutants.
  • a treatment regimen which comprises an aqueous solution of 10% urea and 15% ethylene glycol introduced into an effluent at an introduction rate of 300 ml/hr. and an excess of oxygen of 3.0% has a nitrogen oxides reduction versus effluent temperature curve which is graphically reproduced as FIG. 3c, which graphically reproduces the results of Example IIIc. It will be observed by reference to FIG. 3c that this treatment regimen is operating towards the left side of its curve at an effluent temperature of 1555° F., in the midsection of its curve at an effluent temperature of 1625° F., and towards the right side of its curve at an effluent temperature of 1755° F.
  • the NSR can be increased until the nitrogen oxides reduction is sufficient to attain that level of nitrogen oxides, provided that a maximum level of other pollutants is not surpassed. In this way, if the treatment regimen is operating on the right side of its curve plateau, the target level of NO x is attained while a minimum of other pollutants are produced.
  • the process of this invention can be used to reduce NO x levels while minimizing the production of other pollutants through "load following.”
  • Load following refers to a process which involves adjusting the treatment regimen which is being effected in response to the operating load at which the boiler is being fired.
  • a change in effluent temperature occurs.
  • Such a change in temperature of the effluent it will be apprent, causes the point of operation on the nitrogen oxides reduction versus effluent temperature curve for the current treatment regimen to be translated either to the left, and hence away from minimization of other pollutants, or to the right, potentially off the curve plateau and onto the right side slope of the curve, and hence away from maximum nitrogen oxides reduction.
  • the nitrogen oxides reduction versus effluent temperature curve is shifted (i.e., replaced with a new nitrogen oxides reduction versus effluent temperature curve) so that operation after the change is once again towards the right side of the curve plateau.
  • a change in boiler operating load leads to more than merely a change in effluent temperature.
  • a change in boiler load produces a change in the effluent with regard to NO x level. This becomes especially important when there is a maximum level of other pollutants which has to be met or a target level of nitrogen oxides reduction which has to be attained.
  • the change in NO x level can be measured directly or, preferably, can be determined using a load-dependent boiler characterization factor.
  • the characterization factor relates the NO x level and temperature of the effluent at given locations to boiler load, and it is determined experimentally.
  • the treatment regimen being effected at a given location can be adjusted immediately upon change of boiler operating load as measured by fuel supply rate, for example.
  • the treatment regimen feed rate is reduced to achieve the NSR needed to attain target reductions at that load and the treatment agent components are varied as necessary to respond to the temperature change resulting from the change in operating load. If the feed rate of the treatment regimen were not reduced, the NSR would be excessive in view of the lower level of NO x and excessive NH 3 and CO would be produced.
  • This characterization factor is dependent on boiler geometry, fuel type and boiler load and can be determined experimentally. Several other parameters such as number of burners in service affect the characterization factor, but those that are mentioned above are most important.
  • the nitrogen oxides level and temperature at a given location can be determined to a sufficient degree of certainty to permit the determination of how the treatment regimen should be adjusted to correct for translation on the nitrogen oxides reduction versus effluent temperature curve which occurs when the operating load is changed and for the change in NSR.
  • the preferred embodiment for maximizing nitrogen oxides reduction and controlling the production of other pollutants is by effecting a first treatment regimen which operates at the effluent temperatures currently existing on the right hand slope, off the curve plateau, of the treatment regimen's nitrogen oxides reduction versus effluent temperature curve.
  • a first treatment regimen which operates at the effluent temperatures currently existing on the right hand slope, off the curve plateau, of the treatment regimen's nitrogen oxides reduction versus effluent temperature curve.
  • Another surprising aspect of this invention is in the use of a treatment regimen as a probe for effluent conditions. If the nitrogen oxides reduction versus effluent temperature curve (or, in fact, the ammonia or carbon monoxide production versus effluent temperature curves) for a treatment regimen is known, the effluent condition after that treatment regimen is effected will provide useful information about the effluent condition downstream from the location the treatment regimen is effected, it can even provide information on boiler operating load. For instance, if the nitrogen oxides level is relatively low, but the level of production of other pollutants is relatively high, then it can be assumed that the treatment regimen is operating on the left side of its curve plateau.
  • the effluent temperature can be determined with a reasonable degree of accuracy and, using the boiler characterization factor described above, the boiler load can be determined. Similarly, if the NO x , ammonia and carbon monoxide levels are all low, it can be assumed that the treatment regimen is operating on the right side slope, off the curve plateau, of its curve. Effluent temperature and boiler operating load can then be determined therefrom. The more intimate familiarity with the treatment regimen's curve, the more accurate the determinations can be.
  • the burner used is a burner having an effluent flue conduit, known as a combustion tunnel, approximately 209 inches in length and having an internal diameter of 8 inches and walls 2 inches thick.
  • the burner has a flame area adjacent the effluent entry port and flue gas monitors adjacent the effluent exit port to measure the concentration of compositions such as nitrogen oxides, sulfur oxides, ammonia, carbon monoxide, carbon dioxide, percent excess oxygen and other compounds of interest which may be present in the effluent.
  • the effluent flue conduit additionally has thermocouple ports for temperature measurement at various locations. The temperature of the effluent into which the treatment agents are injected is measured at the location of injection utilizing a K-type thermocouple. Atomizing injectors described in copending U.S.
  • a baseline nitrogen oxides concentration reading is taken prior to beginning each run to calculate the injection ratio of treatment agent to baseline nitrogen oxides and the NSR, and a final nitrogen oxides reading is taken during and downstream from injection of the treatment agents to calculate the reduction in the nitrogen oxides concentration in the effluent elicited by each of the treatment agents injected. Moreover, an ammonia and carbon monoxide reading is taken during and downstream from injection of the treatment agents to calculate the production of other pollutants.
  • Aqueous solutions comprising 10% by weight of urea, 4% by weight of hexamethylenetetramine, 10% by weight of furfural and 0.1% by weight of a commercially available surfactant are injected into the effluent at the indicated temperatures.
  • the results are set out in Table 1 and reproduced graphically in FIGS. 1 and 1a.
  • the treatment agent injected is an aqueous solution which comprises 10% by weight of urea, 15% by weight of furfural, and 0.1% by weight of a commercially available surfactant.
  • the injection temperature, % excess oxygen, NSR, baseline NO x , final NO x and % reduction of NO x for each run is set out in Table 2a and reproduced graphically in FIG. 2.
  • Example IIa The procedure of Example IIa is repeated except that the treatment agent which is injected is an aqueous solution comprising 10% by weight of urea and 0.1% by weight of a commercially available surfactant.
  • the results are set out in Table 2b and reproduced graphically in FIG. 2.
  • Example IIa The procedure of Example IIa is repeated except that the treatment agent injected is an aqueous solution comprising 10% by weight of urea, 15% by weight of ethylene glycol and 0.1% by weight of a commercially available surfactant.
  • the results are set out in Table 2c and reproduced graphically in FIG. 2.
  • Example I The procedure of Example I is followed except that the boiler is fired at a rate of 9.6 lbs/hr. to 10.8 lbs/hr.
  • the treatment agent injected comprises an aqueous solution of 10% by weight of urea, 5% by weight of ethylene glycol and 0.1% by weight of a commercially available surfactant.
  • Table 3a The results are set out in Table 3a and reproduced graphically in FIG. 3a.
  • Example IIIa The procedure of Example IIIa is followed except that the treatment agent injected comprises an aqueous solution of 10% by weight of urea, 10% by weight of ethylene glycol and 0.1% by weight of a commercially available surfactant.
  • the results are set out in Table 3b and reproduced graphically in FIG. 3b.
  • Example IIIb The procedure of Example IIIb is followed except that the treatment agent injected comprises an aqueous solution of 10% by weight of urea, 15% by weight of ethylene glycol and 0.1% by weight of a commercially available surfactant.
  • the results are set out in Table 3c and graphically reproduced in FIG. 3c.
  • a treatment agent comprising an aqueous solution of 10% by weight of urea, 15% by weight of ethylene glycol and 0.1% by weight of a commercially available surfactant is injected into the effluent combustion tunnel described in Example I at a range of NSRs and the production of ammonia measured.
  • the normalized stoichiometric ratio (NSR) for each injection and the results are set out in Table 4 and graphically reproduced in FIG. 4.
  • NSR normalized stoichiometric ratio

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US07/050,198 1987-02-13 1987-05-14 Process for nitrogen oxides reduction and minimization of the production of other pollutants Expired - Lifetime US4780289A (en)

Priority Applications (39)

Application Number Priority Date Filing Date Title
US07/050,198 US4780289A (en) 1987-05-14 1987-05-14 Process for nitrogen oxides reduction and minimization of the production of other pollutants
US07/132,801 US4830839A (en) 1987-02-13 1987-12-14 Ammonia scrubbing
AT88903063T ATE90883T1 (de) 1987-03-06 1988-03-04 Verfahren zur reduktion von stickoxiden mit minimiertem anfall anderer schadstoffe.
PCT/US1988/000724 WO1988006487A1 (en) 1987-03-06 1988-03-04 Process for nitrogen oxides reduction with minimization of the production of other pollutants
HU882855A HUT50294A (en) 1987-03-06 1988-03-04 Method for reducing the content of nitrogen oxides in effluents over and above minimizing the other formation of contaminations
CA000560672A CA1311107C (en) 1987-03-06 1988-03-04 Process for nitrogen oxides reduction with minimization of the production of other pollutants
GB8825253A GB2225001B (en) 1987-03-06 1988-03-04 Process for nitrogen oxides reduction with minimization of the production of other pollutants
YU00448/88A YU44888A (en) 1987-03-06 1988-03-04 Process for reducing nitrogen oxides in exhaust gasses
DE198888903063T DE304478T1 (de) 1987-03-06 1988-03-04 Verfahren zur reduktion von stickoxiden mit minimiertem anfall anderer schadstoffe.
DE88903063T DE3881984T2 (de) 1987-03-06 1988-03-04 Verfahren zur reduktion von stickoxiden mit minimiertem anfall anderer schadstoffe.
EP88903063A EP0304478B1 (de) 1987-03-06 1988-03-04 Verfahren zur reduktion von stickoxiden mit minimiertem anfall anderer schadstoffe
AU14993/88A AU1499388A (en) 1987-03-06 1988-03-04 Process for nitrogen oxides reduction with minimization of the production of other pollutants
PL27105588A PL271055A1 (en) 1987-03-06 1988-03-07 Method for lowering nitrogen oxide and other pollutant content in flue gases
JP50477488A JP2817929B2 (ja) 1987-05-14 1988-05-04 窒素酸化物の減少と他の汚染物質生成の最少化のための方法
DE19883852747 DE3852747T2 (de) 1987-05-14 1988-05-04 Verfahren zur stickstoffoxydminderung und zur minimierung der herstellung sonstiger schadstoffe.
AT88905072T ATE116950T1 (de) 1987-05-14 1988-05-04 Verfahren zur stickstoffoxydminderung und zur minimierung der herstellung sonstiger schadstoffe.
HU883960A HU205586B (en) 1987-05-14 1988-05-04 Process for diminishing concentration of nitrogen-oxides with burning carbon-containing fuels
AU18074/88A AU594299B2 (en) 1987-05-14 1988-05-04 Process for nitrogen oxides reduction and minimization of the production of other pollutants
PCT/US1988/001500 WO1988008824A1 (en) 1987-05-14 1988-05-04 Process for nitrogen oxides reduction and minimization of the production of other pollutants
EP88905072A EP0313648B1 (de) 1987-05-14 1988-05-04 Verfahren zur stickstoffoxydminderung und zur minimierung der herstellung sonstiger schadstoffe
DE1988905072 DE313648T1 (de) 1987-05-14 1988-05-04 Verfahren zur stickstoffoxydminderung und zur minimierung der herstellung sonstiger schadstoffe.
CA 566246 CA1309230C (en) 1987-05-14 1988-05-06 Process for nitrogen oxides reduction and minimization of theproduction of other pollutants
ES8801499A ES2006659A6 (es) 1987-05-14 1988-05-13 Procedimiento para reducir la contratacion de oxidos de nitrogeno en un efluente de la combustion de un combustible carbonaceo.
YU92888A YU92888A (en) 1987-05-14 1988-05-13 Process for reducing nitrogen oxides and decreasing pollution substances arising
PL27242588A PL272425A1 (en) 1987-05-14 1988-05-13 Method for reducing concentration of nitrogen oxides in flue gases with simultaneous reduction in production of other pollutants
DD88315758A DD274171A5 (de) 1987-05-14 1988-05-13 Verfahren zur verringerung der konzentration an stickstoffoxiden in einem abstrom aus der verbrennung eines kohlenstoffhaltigen brennstoffes bei gleichzeitiger minimierung der bildung anderer schadstoffe
PT87493A PT87493B (pt) 1987-05-14 1988-05-13 Processo para a reducao da concentracao de oxidos de azoto e minimizacao da producao doutros poluentes da combustao de combustiveis carbonosos
GR880100315A GR880100315A (el) 1987-05-14 1988-05-13 Μεθοδος ελαττωσεως των οξειδιων αζωτου και ελαχιστοποιησεως της παραγωγης αλλων ρυπαντων
MX1145588A MX167771B (es) 1987-05-14 1988-05-13 Procedimiento para la reduccion de oxidos de nitroeno con reduccion al minimo de la produccion de otos contaminantes
CN88102929A CN1030193A (zh) 1987-05-14 1988-05-14 降低氮的氧化物及使其他污染物产生减至最小的方法
US07/207,382 US4902488A (en) 1987-05-14 1988-06-15 Process for nitrogen oxides reduction with minimization of the production of other pollutants
US07/411,902 US5017347A (en) 1987-02-13 1988-08-12 Process for nitrogen oxides reduction and minimization of the production of other pollutants
DK614888A DK614888D0 (da) 1987-03-06 1988-11-03 Fremgangsmaade til reduktion af nitrogenoxider under minimal fremstilling af andre forurenende bestanddele
FI885103A FI885103A (fi) 1987-03-06 1988-11-04 Foerfarande foer saenkning av maengden kvaeveoxider under samtidig minimering av bildningen av andra foeroreningar.
NO884950A NO884950L (no) 1987-03-06 1988-11-04 Fremgangsmaate for aa redusere nitrogenoxydinnhold under minimal dannelse av andre forurensninger.
DK731788A DK731788A (da) 1987-05-14 1988-12-30 Fremgangsmaade til reduktion af nitrogenoxider og minimering af produktionen af andre forurenende bestanddele
NO89890147A NO890147L (no) 1987-05-14 1989-01-12 Fremgangsmaate for aa redusere mengden av nitrogenoxyder ogminimere dannelsen av andre forurensende bestanddeler.
FI890165A FI88464C (fi) 1987-05-14 1989-01-13 Foerfarande foer minskning av maengden av kvaevets oxider och minimering av bildningen av andra foerorenheter
US07/416,317 US5057293A (en) 1987-02-13 1989-05-23 Multi-stage process for reducing the concentration of pollutants in an effluent

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US07/132,801 Continuation-In-Part US4830839A (en) 1987-02-13 1987-12-14 Ammonia scrubbing
US07/155,864 Continuation-In-Part US4877590A (en) 1987-02-13 1988-02-29 Process for nitrogen oxides reduction with minimization of the production of other pollutants
US07/207,382 Continuation-In-Part US4902488A (en) 1987-02-13 1988-06-15 Process for nitrogen oxides reduction with minimization of the production of other pollutants
US07/411,902 Continuation-In-Part US5017347A (en) 1987-02-13 1988-08-12 Process for nitrogen oxides reduction and minimization of the production of other pollutants
US07/416,317 Continuation-In-Part US5057293A (en) 1987-02-13 1989-05-23 Multi-stage process for reducing the concentration of pollutants in an effluent

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EP (1) EP0313648B1 (de)
JP (1) JP2817929B2 (de)
CN (1) CN1030193A (de)
AT (1) ATE116950T1 (de)
AU (1) AU594299B2 (de)
CA (1) CA1309230C (de)
DD (1) DD274171A5 (de)
DE (2) DE313648T1 (de)
DK (1) DK731788A (de)
ES (1) ES2006659A6 (de)
FI (1) FI88464C (de)
GR (1) GR880100315A (de)
HU (1) HU205586B (de)
MX (1) MX167771B (de)
NO (1) NO890147L (de)
PL (1) PL272425A1 (de)
PT (1) PT87493B (de)
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ATE116950T1 (de) 1995-01-15
NO890147L (no) 1989-01-13
FI890165A (fi) 1989-01-13
HUT56526A (en) 1991-09-30
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WO1988008824A1 (en) 1988-11-17
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CN1030193A (zh) 1989-01-11
DK731788D0 (da) 1988-12-30
FI88464B (fi) 1993-02-15
PT87493B (pt) 1992-09-30
AU1807488A (en) 1988-12-06
DK731788A (da) 1989-01-05
FI88464C (fi) 1993-05-25
HU205586B (en) 1992-05-28
EP0313648B1 (de) 1995-01-11
PT87493A (pt) 1989-05-31
DE3852747T2 (de) 1995-05-18
CA1309230C (en) 1992-10-27
DD274171A5 (de) 1989-12-13
AU594299B2 (en) 1990-03-01
PL272425A1 (en) 1989-03-06
EP0313648A4 (de) 1989-12-12
NO890147D0 (no) 1989-01-12
FI890165A0 (fi) 1989-01-13
GR880100315A (el) 1989-02-23
DE313648T1 (de) 1989-08-03
DE3852747D1 (de) 1995-02-23
YU92888A (en) 1990-04-30

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